Monoazo dyestuffs



. MQNSAZ I) DYESTUFFS Edgar Enders, Leverlrusen-Bayerwerk, Germany, assignor to Farbenfabriken Bayer Aktiengesellschafi, Leverkusen, Germany, a corporation of Germany N Drawing. Application December 15, 1955 Serial No. 553,207

. Claims priority, application Germany December 30, B54

8 (Ilaims. (Cl. 260-446) The present invention relates to metal containing monoazo dyestufis and to a process for their manufacture; more particularly it relates to monoazo dyestuffs corresponding to the following general formula:

The monoazo dyestuffs to be metallized can be obtained by coupling diazotized amines of the benzene series containing a metallizable group in o-position to the diazonium group and which may bear non-ionic radicals in the benzene nucleus, with a 7-hydroxynaphthyl-l-triazine derivative of the general formula Patented Mar. 4, 1958 at an elevated temperature or in an aqueous alkaline solution.

o-Substituted amines of the benzene series suitable as diazo components for the manufacture of the above defined dyestufls are, for example, 1-amino-2-hydroxybenzene, 1-amino-2-hydroXy-5-ch1orobenzene, l-amino- 2 hydroxy 5 nitrobenzene, 1 amino 2 hydroxy- 4 nitrobenzene, 1 amino 2,5 dimethoxybenzene, 1 aminobenzene 2 carboxylic acid, 1 amino 4- or 5 chlorobenzene 2 carboxylic acid, 1 amino 2- hydroxybenzene 5 sulfonic acid amide, 1 amino- 2 hydroxybenzene 5 sulfonic acid methyl amide, l-amino-2-hydroxybenzene-S-sulfonic acid methyl-amide, '1 amino 2 hydroxybenzene 5 sulfonic acid dimethyl amide, l amino 2 hydroxybenzene 5- methylsulfone, 1 amino 2 hydroxybenzene 5 chloromethylsulfone, l amino 2 hydroxybenzene 5- ethylsulfone, the corresponding 1 amino 2 hydroxybenzenel-sulfonic acid amides and l-amino-Z-hydroxybenzene 4 alkylsulfones, l-arnino 2 hydroxy 3- nitrobenzene-S-sulfonic acid amide, l-amino-Z-hydroxy- 5 methylbenzene, 1 amino 2 hydroxy 3 acetylamino 5 methylbenzene, 1 amino 2 hydroxy 3- acetylamino-5-chlorobenzene.

The conversion of the aforesaid metallizable monoazo dyestuffs into cobalt or chromium complexes can be eifected in usual manner, for example by reacting with ammoniacal solutions of cobaltic salts, or with oxalic acid or salicylic acid complexes of trivalent chromium, or with alkali metal chromates in the presence of reducing agents, or with chromium or cobalt. salts in organic solvents.

The chromiumor cobalt-containing dyestufls obtainable according to the present invention are suitable for dyeing animal materials such as wool, silk, leather, as Well as polyamide and polyurethane fibres. They are particularly suitable for dyeing wool from neutral or weakly acid baths, from which they yield level brown, olive or grey shades having very good lightand wetfastness.

The following examples are given for the purpose of illustrating the invention, the parts by weight and the parts by volume being in the ratio of grams to milliliters.

Example 1 18.8 parts by weight of 1-amino-2-hydroxybenzene-5 sulfonic acid amide are dissolved in 250 parts by volume wherein Z has the above significance. Coupling comof water and 18 parts by volume of concentrated hydrochloric acid, and treated dropwise with a solution of 7.0 parts by weight of sodium nitrite in 25 parts by volume of water at 0-5 C. A few drops of a saturated aqueous solution of amidosulfonic acid are added after an hour. The diazo solution thus obtained is slowly run into a solution of 26 parts by weight of 2-amino-4' imino 7 hydroxy 1,5 naphthyl triazine (1,3,5) and 25 parts by weight of soda in 500 parts by volume of water, 500 parts by weight of ice and 20 parts by volume of a 40 percent caustic soda solution. When the coupling is completed the mixture is heated to 60- 70 C., the dyestutf corresponding to the formula 3 V a is completely separated out by addition of common salt and filtered ofi.

The dyestufl? paste is dissolved in 800 parts by volume of :hot .water and, after addition of 300 parts by volume of a chromium salicylic acid solution containing 4.0 parts by weight of-chromium oxide, it. is :heated under reflux until the chroming is complete. The metalrcontaining dyestufi-is completely separated out by addition ofcom- ,mon salt, filtered off and dried. A black .powder is .obtained which dissolves in water with a bluish gray color and dyes wool from a neutral bath in level bluish gray shades of very good fastness to light and washing.

If instead of the diazo component mentioned above there are used corresponding amountsrof 1.-am ino-2-hy-' dIoXybenZene-S sulfonic acid methylarnide 1.-amino-Z- hydroxybenzene-5rsulfonic acid dimethylamide, lamino- 2-hydroxybenzenefi-methylsulfone or l-amino-Z-hydroxy- ,benzene 5-ethylsulfone, dyestuffs are obtained-having similar properties. 7

If insteadof the above said coupling compound there are used corresponding amounts of 2-amino-4-imino-T- hydroxy-l',5-naphthyl-6-methyl- .or -6-hydroxy-triaziue- (1,3,5), dyestuffs are obtained having similar properties.

i 7 Example 2 The dyestutf paste obtained according to the fifstparagraph of Example 1, is dissolved in .800 parts by volume of hot water and treated dropwise with 300 parts by volume .of an ammoniacal solutionof 15 parts by weight of crystalline cobalt sulfateat 90-95" C. The rmetallization is terminated after ashort time/Hie cobalt'containing dyestuii is completely separated out by addition of common salt, filtered oft anddried. Adark powder is obtained which dyes wool from a neutral bath in level reddish gray shades very fast to light and Washing.

Example 3 i 'After the couplingsis completed, the mixture is'heated-to 60-70 C. and the dyestuif, corresponding to the formula is filtered off.

The dyestuif paste is stirred in 2000 parts by volume of hot water and, after an addition of 300 parts by volume V of a chromium salicylic acid solution, containing 4.0 parts by weight of chromium oxide, it is heated under reflux until the metallization is complete. "The dyestuff is completely separated out by addition of common salt, filtered otf and dried; A grayish green powder is obtained which dissolves in waterwith an olive color and dyes wool from a neutral bath in level olive shades very fast to light and washing.

a aszmas 21.6 parts by weightof 1-amino-2-hydroxybenzene-4- sulfonic acid dimethylamide in 400 parts by volume of waterand 18 :parts .by volume of concentrated hydrochloric acid arediazotizedwith 7 .O'parts by weight of sodium nitrite in 25 parts by volume of water; the diazo solution thus obtained is run into a solution of 26 partsby weight of 2-amino-4-imino-7 -hydr ox y 7 1'5 naphthyltri-azine- (1,3,5) and 25 parts by weight of soda in 500 parts by volume of water, 500 parts by weight of ice 1111120 parts by volume of a 40 percent caustic soda solution. When the coupling is completed, the mixture is heated to 60-70 C., and the dyestufi corresponding to the formula The dyestuff paste thus obtained is dissolved in 1500 parts by volume of hot water. .250. parts by volume of volume of a saturated common salt solution are run into it, the chromium containing dyestuif is filteredotr' and dried. e A dark powder is obtained which dyes wool from a neutral bath in level greenish gray shades having very good fastness to light and water.

The cobalt complex of the same dyestufi dyes wool from a neutral bath in fast bluish gray shades.

' Example 5 13.7 parts by weight of l-aminobenzene-Z-carboirylic acid in 250 parts by volume of water and 18 parts by volume :of concentrated hydrochloric'acid are diazotized with 7.0 parts by weight of sodium nitrite in 25 parts by volume of water; the dia'zo solution thus obtained is run into a solution of 26 parts by weight of 2-amino-4-.

imino-7'-hydroxy-1',5-naphthyltriazine (1,3,5) and 25 parts by weight of soda in 5 00 parts by volume of water, 500 parts by weight of ice and 20 'parts by volume of a 40 percent caustic soda solution. After the coupling is completed, the mixture is heated to 60-70 C. and the dyestufi of the following formula,

is completely separated out-by addition of eommon'zsalt and filtered off. The jdyestufi paste thus obtained is added to 300 parts by volume of dimthylformamide; a concentrated aqueous chromium formate solution, containing 4.5 parts by weight of chromium 'xide,'is added and the mixture is stirred at 125C. for several hours. After cooling, the mixture is run into 1000 parts by volume of a saturated common salt solution, the separated chromium-containing dyestuif is'filtered oif, Washed with common salt solution, mixed with parts by weight of trisodiumphosphate and dried.

A dark brown powder is obtained which dissolves in water with a brown color and dyes wool from a neutral bath in very level, reddish dark-brown shades having very good fastness to light and washing.

Example 6 15.3 parts by weight of 1-amino-2,5-dimethoxybenzene are dissolved in 400 parts by volume of Water and 18 parts by volume of concentrated hydrochloric acid and diazotized with 7.0 parts by weight of sodium nitrite in 25 parts by volume of water. The diazo solution thus obtained is run into a solution of 26 parts by weight of 2 amino 4 imino 7' hydroxy 1,5 naphthyl tri amine-(1,3,5) and 25 parts by weight of soda in 500 parts by volume of water, 500 parts by weight of ice and 20 parts by volume of a 40 percent caustic soda solution. After the coupling is completed, the mixture is heated to 60-70 C., and the dyestufi of the following formula 4} OCH: =NH

N N=N OH OH:

is filtered OE and dried.

The dyestufi powder thus obtained is introduced into 300 parts by volume of dimethylformamide; a concentrated aqueous chromium formate solution, containing 4.5 parts by weight of chromium oxide, is added to it and the mixture is stirred at 130-135 C. for several hours until the metallization is completed. The mixture is run into 1000 parts by volume of a saturated common salt solution, the separated chromium containing dyestuff is filtered off, stirred with dilute caustic soda solution, again filtered ofi and dried.

A dark powder is obtained which dyes wool from a neutral bath in level grayish green shades having very good fastness to light and washing.

I claim:

1. Dyestuffs selected from the group consisting of monoazo dyestuffs corresponding to the general formula:

OHX

wherein X stands for a member selected from the group consisting of a hydroxy, lower alkoxy and a carboxyl group, Y means a radical selected from the group conand the chromium complex thereof.

5. A dyestuff selected from the group consisting of the monoazo dyestuif corresponding to the following formula:

OH H

and the chromium complex compound thereof.

6. A dyestutf selected from the group consisting of the monoazo dyestutf corresponding to the following formula:

ll SIO2.C2H5

and the chromium complex compound thereof.

7. A dyestuff selected from the group consisting of the monoazo dyestulf corresponding to the following formula:

and the chromium complex compound thereof.

8. A dyestutf selected from the group consisting of and the chromium -comple'x compound thefeQif; 

1. DYESTUFF SELECTED FROM THE GROUP CONSISTING OF MONOAZO DYESTUFF CORRESPONDING TO THE GENERAL FORMULA: 